Ammoxidation process

ABSTRACT

A process for vapor phase ammoxidation of hydrocrbons which comprises reacting vapors of ammonia and said hydrocarbon in the presence of a molten salt eutectic mixture of V2O5 and K2O, said molten salt being atomized in the presence of said ammonia and hydrocarbon, and, optionally, said spent molten salt being regenerated by air oxidation and recycled for reuse. The invention also embodies an apparatus for the ammoxidation process which comprises a reactor vessel fitted with (a) input means for ammonia and hydrocarbon, (b) an atomizing apparatus within said reactor, (c) means for feeding the molten eutectic salt from an upper reservoir to said atomizing apparatus, (d) a lower reservoir for spent molten salt, and (e) a gas-lift to move said spent salt from said lower reservoir to said upper reservoir.

United States Patent [19] Shang et al.

[ 1 Nov. 5, 1974 AMMOXIDATION PROCESS [75] Inventors: Jer-Yu Shang, Wilmington, Del.;

Raymond Wynkoop, Gladwyne, Pa.

[73] Assignee: Sun Research and Development Co.,

Philadelphia, Pa.

22 Filed: Sept. 6, 1972 [2!] Appl. No.: 286,634

{52] U.S. Cl. 260/465 C, 23/288 R, 26l/78'R,

252/476 [51] Int. Cl. C07c 121/02 [58] Field of Search 260/465 C [56] References Cited UNITED STATES PATENTS 3/l972 Riegel et al 260/465 X OTHER PUBLICATIONS Holtzberg, J.A.C.S., Vol. 78, p. 1538 (1956).

Primary Examiner-Lewis Gotts Assistant ExaminerDolph H. Torrencc Attorney, Agent, or Firm-George L. Church; Donald R. Johnson; Paul Lipsitz [5 7] ABSTRACT carbon, (b) an atomizing apparatus within said reactor, (0) means for feeding the molten eutectic salt from an upper reservoir to said atomizing apparatus, ((1) a lower reservoir for spent molten salt, and (e) a gas-lift to move said spent salt from said lower reservoir to said upper reservoir.

.9mm. 1 raws Fi AMMOXIDATION PROCESS It has been disclosed in the application of William C. Neikam et al., Ser. No. 267,303, filed June 29, 1972 that ammoxidation reactions may be carried out with V as catalyst where the V 0 is employed in the form of a molten eutectic with K 0. The eutectic melts at 390C and consists of 39 mole percent of K 0 and 61 mole percent of V 0 It is made simply by heating such a molar mixture slowly with stirring to about 500C, CO being evolved and the eutectic formed. This eutectic is described in an article by l-loltzberg, J.A.C.S. 78 p. 1538, 1956.

This invention provides an improved process for carrying out ammoxidation reactions using the abovedescribed eutectic as catalyst. in accord with this invention, there isprovided a process for vapor phase ammoxidation of hydrocarbons which comprises reacting vapors of ammonia and said hydrocarbon in the presence of a molten salt eutetic mixture of V 0 and K 0, said molten salt being atomized in the presence of said ammonia and hydrocarbon. In a preferred process, the spent molten salt is regenerated by air oxidation and recycled for reuse. The invention also embodies an apparatus for the ammoxidation process which comprises a reactor vessel fitted with (a) input means for ammonia and hydrocarbon, (b) an atomizing apparatus within said reactor, (c) means for feeding the molten eutectic salt from an upper reservoir to said atomizing apparatus, (d) a lower reservoir for spent molten salt, and (e) a gas-lift to move said spent salt from said lower reservoir to said upper reservoir.

The organic reactants useful in the process may be selected from a wide variety of compounds and will include alkyl-substituted aromatic, aliphatic and alicyclic compounds. Among preferred starting materials are the monoand polyalkyl-substituted aromatic hydro-' carbons such as toluene, the xylenes, a-methylnaphthalene, polymethylnaphthalenes, mono-alkyl and polyalkyl anthracenes, mesitylene, durene, and the like. The alkyl substituent may, of course, contain more than a single atom and thus the corresponding ethyl and other lower alkyl substituents are also useful.

Aliphatic compounds normally subjected to ammoxidation include the olefinic compounds. Thus, any olefinic hydrocarbon having at least one alkyl group is useful in the process. Examples of such compounds are propylene, butenes, octenes, methyl heptenes, alkylbutadienes, pentadienes, ethyl butenes, hexadienes, heptadienes, and the like, all of which will give the corresponding nitriles. Preferred olefins are those containing up to about ten carbon atoms, particularly propylene, butenes, and the methylbutadienes and cycloolefinic compounds, particularly the alkyl-substituted hydrocarbon olefins exemplified by 3-methyl cyclohexene, 3,6-dimethyl cyclohexene, methyl tetralin and the like.

Also of value as reactants are alicyclic compounds having an alkyl substituent and these compounds are exemplified by methylcyclopentane, methylcyclohexane, the alkyl-substituted decalins, and the like.

In order to further describe the invention, reference is now made to the drawing and for illustrative purposes the process described will refer to the reaction of meta-xylene and ammonia to yield isophthalonitrile.

'In accord with the drawing, ammonia and m-xylene are introduced to a reactor 11 through an input line 12,

the mixture of gases passing through a nozzle 13. This nozzle may be of a variety of atomizing devices and is preferably an atomizing type using high intensity sound waves. The nozzle used will provide means for the molten catalyst of the V O /K O eutectic 14 to enter the sonic energy field 13a in order that thorough atomization of the reactants and catalyst occur thus effecting a highly efficient contact and reaction system. Such a nozzle is described in US. Pat. No. 3,371,869 and is commercially available under the trade name Sonicore from Sonic Development Corporation. The molten eutectic 14 is held in an upper reservoir 15 and is fed into the sonic area of the nozzle through an opening 16 controlled by a valve 17, the rate at which the molten eutectic drops into the nozzle depending upon the size of the opening. The spray from the nozzle may be directed at an optional baffle 18, which will aid in separating the eutectic from the gaseous products. The products of isophthalonitrile, unreacted ammonia, and any by-products are taken overhead through a vent 19 to a separation and product recovery system which may be a series of cyclones (not shown) or other applicable system.

The molten spent eutectic catalyst drops to the bottom of the reaction chamber 11 and is maintained as a, liquid lower reservoir 20. Extending from above they bottom of the lower reservoir to a level in the upper reservoir 15 above the molten eutectic is a conduit 22 which serves as a gas-lift and regeneration system for the spent eutectic. Air or other oxygen containing gasv is fed into the gas-lift conduit 22 through inlet 23 which is inside and concentric with the conduit and in this way the molten eutectic 21 near the opening of the gaslift conduit is swept into the gas-lift and transported upward to spill over the conduit into the upper reservoir 15. During its passage through the conduit 22 the oxygen in the lift-gas effects regeneration of the spent eutectic so that it is again ready for use. The lifting gas exits overhead through vent 24.

It will be understood that various alternativemethods are useful within the context of the above-described apparatus. For example, the eutectic may be atomized by passing an inert gas through the sonic nozzle and the ammonia and hydrocarbon gases fed intothe reaction system separately. Means other than the illustrated valve 17 may be used to feed the molten eutectic to the atomizing nozzle and other modifications will be evident to the skilled art worker.

Because the molten eutectic is highly corrosive it is important that corrosion resistant materials be used to about 500C, the usual ammoxidation temperature range. Reaction pressure is preferably atmospheric pressure, although higher and lower pressures may be used (e.g., from about 0.5 to about 20 atmospheres).

The products of the reaction, together with any unconverted reactants, after removal from the reactor are separated by conventional methods, any unreacted hydrocarbon being recycled to the reactor, if desired. Similarly, recycle of partially ammoxidized hydrocarbons (e.g., m-' or p-xylene converted to mor ptoluonitrile) may be recycled for further conversion to polynitriles. The ratio of ammonia to xylene to hydrol. A process for the vapor phase ammoxidation of hydrocarbons to nitriles which comprises reacting vapors of ammonia and said hydrocarbon under ammoxidation conditions in the presence of a molten salt eutectic mixture of V 0 and K 0, said molten salt being atomized by a nozzle in the presence of said ammonia and hydrocarbon.

2. The process of claim 1 where the spent molten salt is regenerated by oxidation and is recycled for reuse.

3. The process of claim 2 where the hydrocarbon is an aromatic hydrocarbon.

4. The process of claim 3 where the hydrocarbon is xylene.

5. The process of claim 1 where the nozzleis a sonic nozzle.

6. The process of claim 5 where the hydrocarbon is xylene. 

1. A PROCESS FOR THE VAPOR PHASE AMMOXIDATION OF HYDROCARBONS TO NITRILES WHICH COMPRISES REACTING VAPORS OF AMMONIA AND SAID HYDROCARBON UNDER AMMOXIDATION CONDITIONS IN THE PRESENCE OF A MOLTEN SALT EUTETIC MIXTURE OF V2O5 AND K2O, SAID MOLTEN SALT BEING ATOMIZED BY A NOZZLE IN THE PRESENCE OF SAID AMMONIA AND HYDROCARBON.
 2. The process of claim 1 where the spent molten salt is regenerated by oxidation and is recycled for reuse.
 3. The process of claim 2 where the hydrocarbon is an aromatic hydrocarbon.
 4. The process of claim 3 where the hydrocarbon is xylene.
 5. The process of claim 1 where the nozzle is a sonic nozzle.
 6. The process of claim 5 where the hydrocarbon is xylene. 